This invention relates to 2,2-dimethyl-4(2' or 4'-pyridyl) butyronitriles, methods of preparing same and uses thereof in augmenting, imparting or enhancing aromas in or to perfume compositions, perfumed articles and/or colognes.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product.
Long-lasting substantive green, new mown hey, fresh lilac, minty and herbaceous aromas with minty and new mown hey undertones are highly desirable in several types of perfume compositions, perfumed articles and colognes (e.g., piney fragrances).
The perfume uses of nitrile-contraining derivatives are well known in the prior art. Thus, the compound having the structure: ##STR3## is shown to be useful in perfumery in U.S. Pat. No. 4,837,351 issued on Jun. 6, 1989 wherein it is indicated that it has a powerful fresh, fruity, floral odor note accompanied by a citrus, green topnote. Furthermore, U.S. Pat. No. 3,325,369 discloses the use of cinnamonitrile as a material useful in augmenting or enhancing the aroma of perfume compositions.
Other nitriles containing gem-dimethyl moieties "alpha" to the cyanide moiety are disclosed in Blumenthal, et al, U.S. Pat. No. 3,168,550 issued on Feb. 2, 1965.
Nothing in the prior art discloses the use in perfumery of the 2,2-dimethyl-4(2' or 4'-pyridyl) butyronitriles of our invention.
The preparation of phenyl butyronitriles are taught in the prior art to be rather complex and costly. Thus, 2,2-dimethyl-4-phenyl valeronitrile is shown to be prepared according to the reaction: ##STR4## using a chromium carbonyl complex by Semmelhack, et al, J. Am. Chem. Soc., 1980, 102, 6584-6586.
The preparation of 2,2-dimethyl-4-phenyl(2' pyridyl) butyronitrile having the structure: ##STR5## is disclosed in Magnus, et al, J. Am. Chem. Soc., Volume 78, (1956) at pages 4127 and 4130. The reaction shown thereat is: ##STR6## using a sodium metal catalyst (and not the catalyst disclosed and claimed in the instant application). The Magnus, et al reference is abstracted at Chem.Abstract, Volume 51, column 3595 g. Magnus, et al also discloses the reactions: ##STR7## to produce, respectively the compounds having the structures: ##STR8## Nothing in the prior art discloses the use of sodium hydride or lithium diisopropyl amide having the structure: ##STR9## as a catalyst for carrying out the reactions: ##STR10##
Furthermore, considerable difficulties have heretofore been encountered in using compounded hypochlorite bleach or sterilizing solutions with perfumed oils so that a stablelong-lasting, single phase commercially feasible bleach or sterilizing solution has been difficult to obtain, particularly wherein the desired aroma of the article bleached or sterilized (e.g., clothing) has a pleasant and stable and consistent aroma on drying (and not the usual "hypochlorite-bleached-article" aroma). The problem has been defined in United Kingdom Patent Specification No. 886,084 published on Jan. 3, 1962 wherein it is stated that a stable "dispersion" of hypochlorite-resistant perfume in aqueous solutions of hypochlorites was formulated. United Kingdom Patent Specification No. 886,084 discloses the preparation of an aqueous solution of a hypochlorite containing a hypochlorite resistant perfume and a surface active quaterary ammonium compound of the betaine type soluble in the hypochlorite solution. Such ammonium compounds have the generic structure: ##STR11## wherein each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are alkyl. One of the features of the perfumed solution produced in accordance with said United Kingdom Patent Specification No. 886,084 is indicated to be that the solution exhibits foaming properties. Another feature of United Kingdom Patent Specification No. 886,084 is stated to be that the perfumed solutions covered by the patent are found to be clear and homogeneous after eight weeks of storage at room temperature. Nevertheless, betaines such as ":Ambiteric D" as are discussed therein are not so broadly useful when used in concentrations of from 0.15% up to 4.0% (based on total weight of bleach or sterilizing solution) as to have the ability to be used in conjunction with perfume oils which should be incorporated into thickened, high viscous hypochlorite bleaches or sterilizers having excellent surface tension properties so that long-lasting stable soluble single phase thickened perfumed aqueous alkali metla hypochorite bleach or steriling solutions having the long-lasting pleasant stable aromas are obtained, particularly where the quantity of perfume oil in the bleach or sterilizing substance is at levels of between 0.02% and 0.8% by weight of the total bleach or sterilizing solution. The need for such aromas (e.g., "citrusy") to be present in such bleach or sterilizing solutions exists so that the disagreeable characteristic "hypochorite" aroma is substantially eliminated from aromas of the end product to which the bleach or sterilizing solution is applied; particularly on dry-out, as well as from the aroma of the hands of the user when they in direct contact with such bleach or sterilizing solutions.
U.S. Pat. No. 3,560,389 also discloses the feasibility of using perfume oils in hyposchlorite bleaches or sterilizers at column 3, lines 37-40 but the disclosure is limited to inclusion of various detergents in addition to amine oxides, such as lithium lauryl sulfate and sodium lauryl ether sulfate and/or is further limited to include hydrotropes such as socium xylene sulfonate in addition to the amine oxide. Exclusion of such hydrotropes and detergents additional to the amine oxides and diphenyl oxide derivatives of our invention is desirable not only to cause the phenyl butyronitriles of our invention to function properly but also from an ecological standpoint.
European Chemical News, Volume 13, Jan. 18, 1968, sets forth a synopsis of South African Patent No. 67/4667 which corresponde to U.S. Pat. No. 3,560,389, but the reference also states at page 42:
"Alternatively, a detergent with bleaching or bacteriocidal properties can be formulated. Perfuming bleaching solutions is not possible." PA1 "Claim: An aromatic liquid bleaching composition containing, as active ingredient, sodium, hypochlorite, which comprises one or more of simple perfumes or compounded perfumes selected from the group consisting of anisole, benzophenone, benzylphenyl ether, bromelia, cedrenyl acetate, p-tertiary butylcyclohexanol, dimethylbenzylarbinyl acetate, dihydroterpinyl sacetate, diphenyl oxide, dimethylbenzyl carbinol, dimethylphenyl, carbinol dihydroterpineol, fenchyl acetate, fenchyl alcohol, p-methyldimethylbenzylcarbinol, methylphenylcarbinyl acetate, methyl-n-valerate, muskmoskene, muscarone, methylamyl keton, phenylethyldimethylcarbinyl acetate, rose phenone, styrallyl propionate, tetra-hydromuguol, tetra-hydromuguyl acetate, tertra-hydrolinallol, tetrahydrolinalyl acetate, verool, veleton, verdox, coniferan and yarayara, and a surface solution of sodium hypochlorte."
Neither the South African nor the United States Patents, however, indicate the advantages and usefulness of limiting the detergents either to (a) compounds having the generic structure: ##STR12## wherein at least one of R.sub.1 and R.sub.2 represents C.sub.10 -C.sub.12 straight chain or branched chain alkyl and when one of R.sub.1 or R.sub.2 is C.sub.10 -C.sub.12 branched or straight chain alkyl, the other of R.sub.1 or R.sub.2 is pH-adjusted hydrogen and wherein M.sub.60 and M.sub.62 are the same or different and each represents alkyl metal which may be sodium, lithium or potassium, or (b) to mixtures of compounds having the structure: ##STR13## with at least one amine oxide defined according to the structure: ##STR14## of excluding from the formulation a hydrotrope or of specifying the nature of the perfume oil useful in the perfumed bleach or sterilizing solution (wherein A and B are each separately methyl or taken together, complete a morpholino ring and wherein R.sub.3 is straight chain alkyl having from 11 up to 13 carbon atoms).
U.S. Pat. No. 3,876,551 in attempting to solve the foregoing problem discloses a stable single phase aqueous alkyl metal hypochlorite liquid perfume bleach or sterilizing composition comprising an aqueous mixture of (1) an amine oxide composition consisting essentially of at least one morpholino and/or dimethyl (C.sub.11 -C.sub.13 straight chain alkyl amine oxide in an amount greater than 55% of said amine oxide composition, (2) at least one alkali metal hydroxide, (3) at least one alkali metal hypochlorite, and (4) a perfume oil compatible with the mixture capable of imparting a "woody" or a "floral" or a "clean fresh" or a "citrusy" note to the bleach or sterilizing compositions; the mixture having a pH in the range of from 12 to 13.5 and the mixture excluding hydrotropes as well as all surfactants except the amine oxide. U.S. Pat. No. 3,876,551 also attempts to solve the foregoing problem by disclosing a process for producing the above-named mixture comprising the steps of combining an amide oxide composition consisting essentially of one or more morpholino and/or dimethyl C.sub.11 -C.sub.13 straight chain alkyl amine oxide(s) with the perfumed oil to form an amine oxide-perfume oil premix; admixing the amine oxide-perfumed oil premix with an aqueous alkali metal hypochlorite solution, and combining an alkali metal hydroxide with the solution whereby the final pH of the mixture is from 12 up to 13.5. In a further effort to solve the foregoing problem U.S. Pat. No. 3,876,551 also discloses adjustment of the pH of the aqueous metal hypochlorite solution initially to the range of 12-13.5 and then combining the resulting aqueous hypochlorite solution with the aforementioned premix. The resulting composition is indicated to cause products to which said composition is applied to have eliminated therefrom the disagreeable characteristics "hypochlorite" aroma and instead to have a "clean fresh" or "floral" or "woody" or "citrusy" aroma to be imparted to the treated products. In addition, it is stated that the hands of the individual user after using and being in direct contact with the hypochlorite composition will not have the disagreeable characteristics "hypochlorite" aroma but instead will have a plesant "clean fresh" or "floral" or "woody" or "citrusy" aroma.
The disadvantage of the system of U.S. Pat. No. 3,876,551, however, concerns (a) the inability to use a thickener in the system whereby the resulting liquid has a viscosity of 5-25 centiposes at 20.degree.-40.degree. C. and (b) the relative chemical stability and substantive stability of the perfume oil and of the single liquid phase system. Nothing in U.S. Pat. No. 3,876,551 indicates such a high degree of stabilities of the perfume-hypochlorite system as exists in the system of the present invention; wherein there is also included a thickener. Indeed, the stabilities using the system of the instant invention are far greater even at levels as low as 3% hypochlorite and are also relatively stable (from a standpoint of chemical stability of perfume oil, substantive stability of perfume oil and phase separation stability taken in combination with one another) at levels of as high as 10% hypochlorite in aqueous solution. Thus, the instant system gives rise to unexpected, unobvious and advantageous properties over the system taught in the prior art.
Furthermore, nothing in the prior art including the teaching of U.S. Pat. No. 3,876,551 states either explictly or implicitly the compatability of a thickener in the instant system, such as sodium palmitate, sodium stearate, potassium, palmitate, potassium stearate, lithium palmitate, lithium stearate, lithium laurate, potassium laurate or sodium laurate whereby a stable gel (as opposed to a liquid) phase perfumed hypochlorite system or perfumed oil stabilizer emulsifier system "premix" may be produced.
The combination of the compound group having the structure: ##STR15## (wherein R.sub.1, R.sub.2, M and M.sub..beta. are defined, supra) with perfume and hypochlorite bleach in general, is set forth in the Kao Soap Company, Japanese Patent No. 25514/79 filed on Nov. 2, 1973 and opened for public inspection on Jun. 19, 1975. Thus, on page 2, at column 4, line 15, the compound: ##STR16## is disclosed for use in conjunction with the perfumed hypochlorite bleaches. The claim of the Kao Soap Patent is as follows:
Furthermore, the use of such compounds as those having the structure: ##STR17## (wherein R.sub.1, R.sub.2 M and M.sub..beta. have been previously defined) with the hypochlorite bleaches is documented in the brochure of Dow Chemical entitled "DOWFAX.RTM. Surfactants" and is covered in the Dow Chemical Company U.S. Pat. No. 3,172,861 issued on Mar. 9, 1965.
The 2,2-dimethyl-4(2' or 4'-pyridyl) butyronitriles of our invention are unique insofar as the aforementioned system are concerned for use in hypochlorite bleaches. Nothing in the prior art discloses organic compounds having a structure like any of the 2,2-dimethyl-4(2' or 4'-pyridyl) butyronitriles of our invention for use as stable aroma imparting, augmenting or enhancing agents in hypochlorite bleaches.